Manufacture of alcohols.



' waiter.

Ito Drawing.

BENJAMIN r; nnooxs AND HARRY Essex, or PITTSBURGH, PENNSYLVANIA, AS51631- \TIONOE Texas.

To all whom it may concern:

Be it known that we, BENJA IN T. Bnooxs and HARRY Essex, citizens o the United States, and residents of Pittsburgh,in the county of Allegheny and State of Pennsylvania, have invented certain new and useful Improvements in the Manufacture of Alcohols, of which the following is a specification.

. This invention relates to the manufacture of alcohols; and it comprises a method of making amyl (pentyl) alcohol and other high boiling monohydric alcohols containing five or more carbon atoms from the corresponding chlorids, wherein said chlorids are heated, such heatizg' being best done under pressure, with mixture comprising methyl alcohol and a formate, thereby producing methyl formate, a chlorid and the desired higher alcohols, the reaction mixture being subsequently treated to recover the excess of methyl alcohol, the methyl formate and the excess of the formate used, as

well as the alcohols produced, such inethyl formate being subsequently reconverted into a formate and methyl alcohol for reuse, such process being particularly adapted to the manufacture of commercial amyl alcohol or fusel oil from chlorinated fractions of gasolene or other low boiling petroleum oils; all as more fully hereinafter set forth and as claimed.

Fusel oil, which for the present pur of alcohols containing more and less carbon,

is a material of high price, the natural source of supply being practically limitedand have elsewhere described, materialsto certain fractionsobtained in the manu-- facture of grain alcohol. As we have found,

may be made from certain ga'solene fractions which are composed very largely of the monochlor substitution products of the hydrocarbons containing five carbonatoms. Usually, these. materials .also contain, to a less extent, chlorin substitution products of\higher ;and; lower hydrocarbons. -The amount of these other products will depend of course upon the accuracy withwhich the fractionation of the original; gasolene or like oil is conducted. Suitable raw, mate' rials for this purpose may be made by fracr Specification of Letters Patent.

Application filed March 22, 1916. Serial No. 5,957.

' with various reagents.

ons T0 euLr nnrININe COMPANY, or rrrrsiaungn, rn 'NsYLvaNIan oonfroaa.

MANUFACTURE or nncono'ns.

Patented Apr. 3,

tioning commercial gasolene' to obtain the portions distilling from to C. Other suitable materials may be made by producing similar fractions from what is known as casing head gasolene. By propercare in chlorination (see application of Brooks, Es-

sex and Smith, Serial No. 65,826, filed Decem ber'8, ,1915; patented July 18, 1916, Ser.

No. 1, 191,916) thesefractions, which may hereinafter be termed low boiling gasolenes for the sake of a name, may be converted into monochlor derivatives; that, is, intobodies which differ from the original hydro,

carbons by the entry of one chlorin atom,

and only one,'in the molecule in substitution for a hydrogen atom. The monochlor substitution products obtained from the stated gasolene fractions will generally boil between around 95 and 140 C. It is monochlorinated material of this nature which disadvantageous for the .present purpose since the presence of certain amounts of otheralcohols is desirable in ainyl alcohol (fusel oil) for commercial purposes; There are a number of. monochlor derivatives of the various pentanes and/these chlorin derivatives differ materially in their action On treatment however with many organic salts of the alkali metals, such as the acetate of sodium, they may be converted into the corresponding esters, such as the acetates. I In this conversion into acetates, as we have elsewhere de:

scribed and claimed, (see our application 65708, filed December 8, 1915) the conversion is very much facilitated land the amount of product enhanced by mechanically agitating the mixture duringthe action.

These processes however, as stated, give esters (acetates) of the amyl alcohols and number of purposes the amyl alcohols, rather than their esters, are desirable. It is in practice however considerably more difficult for the. reason that the action of alkalis ,not the amyl alcohols themselves. For a stead of re esent ng,

upon these monochlor substitution. products from simple direct saponification, only certain of the chlorin substitution compounds compounds.

' methyl alcohol, to form corresponding chlorid.

conversion of the formate mate and regard it as probable.

represents substantially all these chlorin stated chlorinated gasolene fractions, Qare heated together with a lower alcohol, which of the reactiomgoing forward to produce the amyl esters, an entirely different reaction takes place.- The formic acid of the formate 'combines with the methyl alcohol to yield with the etalof the formate to form the In ghis action, the amyl chlorids, and the 0th r high boiling chlorids, form amyl and other alcohols. The gross result of the action-thereforeis the into a chlorid; of a largeportion of the into the c'orrespondin forv the production of amyl and other high boiling alcohols; It is probable that in this reaction the first result is the forma:

the conversion methyl alcohol tion .of an amyl formate which then againbreaks up, by double exchaiige with the methyl formate and we do not limit our the higher alcohol {but action although we selves to this theory of said that the aflinity of the methyl alcohol for-the formic acid is greater than that of the amyl alcohol so thatwhen the amyl ch10 rid reacts withthe formate to produce anfyl v formate and the chlorid, the amyl formate is then again broken up by the methyl alcohol ormate.

, however, this is theory. There appears to be hols and methyl alcohol which is the most a balanced reaction and as we have-found, if

sufficient methyl alcohol and suflicient formate are present, we obtain the amyl alcomethyl formate. We find that as a rule it is desira le to use somewhat more formate than corresponds to the amyl chlorids; say a molecule and a quarter or am'olecule'and a half. We ordinarily employ five times as many-gallons as there are gallons of the liquid chlorination" product treated; We find that sodium formate, available. formate comthat calcium formate,

. et'c., may'also be employed.

as does the product We have found that where 'chlorinated pentanes and the like, or the geraturep We etween, say, 140

wlrolebest adapted. The pressure niay be is best'methyl alcohol, and aformate, instead h ate while the clflorin combines.

reaction is practically In a Wayfit may be:

As stated,

111 the proportion of four mercially, is also the best adapted for the presentpur'poses since it cofnbines an an hydrous nature with ,a considerable degree of solubility in the fluids placed in reaction. This solubility isconvenient for a number of reasons later appearing. We shall therefore hereinafter speak more specifically of sodium formate while wishing it understood potassium formate,

.Whilethe stated production-of amyl alcohol will take nlacexat a variety oftempera-v tures and under a variety of conditions, it being indeed possible to effect the reaction.

under a .well cooled reflux condenser, yet' for'the sake of speed and a variety of other reasons it, is best t v under pressure and at a relatively high temfind that a temperature range C; and 190 C. is on t e t at corresponding to t e temperature. Methyl alcohol boils at 66'to 67 C. while the .methyl formate, which is one of the products 0 the reaction, boils at about 39r-33 6., so thatv the progress of the reaction'may be followed by watching the indications of a pressure gage.- is being produced, the temperature remaining the same, the pressure will tend to rise.

en the pressure remains stationary, the

finished. The reaction is very much accelerated and the product is rendered greater by a rotation of the container during the operation. As to the exact reason for this improvfiement in speed and yield we are not pos probably in part due to the thorough admixture of the liquids, to the maintenance of the" concentration of the dissolved forive; but it is mate in the reaction liquids, to friction exposing fresh surfaces of by the liquids, etc. After the reaction is complete, the reac-' tion liquid will contain methyl formate, the excess of methyl alcohol and most or all of theJexc'ess of the formate employed, if this formate be sodiumformate. It also contains the amyl and other alcohols produced by the reaction. The chlorid, as for example sodium chlorid, produced is notsoluble to any extent in the reaction liquidiand remains as a crystal powder. 'After t e heatformate for action ing the reaction liquid may be cooled, sepa-- salt and fractionally disrated from the tilled.- The methylformate and the methyl alcohol may be'collected togetheror separated as may be desired: -After distilling off the methyl formate and the methyl alcohol, the fusel oil (that is the mixture of amyl alcohols with other high boiling formed) may be distilled ofl'. contaihs the excess of sodium formate which may be reused. The crystalline mass of the salt separated from the o perform the process:

alcohols he residue As long as .methyl formate reaction liquid on f? cooling contains but little formate. If it be desired to recover this formate it may be done by fractional crystallization or by extraction with hot methyl alcohol. methyl formate may be saponified with soda or sodium carbonate to regain sodium formate and methyl alcohol. If the methyl alcohol and methyl formate are separated in the original distillation, the mixture may be thelike, to produce a mixtureof hydrocarbons boiling between ant 45 C. or thereabout. If we wish ultimately a larger pro.-

portion of low boiling alcohols, these gasolene fractions may be taken from 29 0. up and similarly if we "desire a larger proportion of alcohols still higher boiling than amyl alcohol, we may take a somewhat higher boiling gasolene fraction; say up to 50 or C. In this connection it may be stated that while we consider .our invention as more particularly applicable ,to the production of an artificial or synthetic fusel oil of the same properties and composition as the ordinaryfusel oil f commerce, which is a mixture of amyl lcohols containing more or less of the butyl alcohols and of the hexyl alcohols, yet it is by no means restricted thereto and may be applied to the production of other high boiling alcohols; as for example, the production of'alcohol mixtures consisting mainly of butyl alcohol; or of hexyl alcohol. Heptyl, octyl, etc.-, alcohols may also be so prepared. 4

Our process is also of'course applicable to the aftreatment of chloninated products obtaind from the pure hydrocarbons such as normal pentane, isopentane, etc.

Having obtained the stated gasolene fraction, we next chlorinate it by a regulated action of chlorin thereon in thepresence of a controlled source of actinic light. Generally the chlorination is so conducted as to and the chlorinated products are then separated from the remaining hydrocarbons by fractional distillation. Being higher bo1l1ng than thehydrocarbons from which they are derived,this separation is easy. The remaining-iunchlorinated fraction 'gof the hydrocarbons is again treated withchlorin.

Having'obtained the monochlor derivatives, we place the material, which is in liquidiform, in any suitable apparatus. We regard, asstated, an apparatus capable of rotation as being othe "best adapted for our 7 purposes. To this'material is added methyl alcohol in. the proportion 'of about-3 or 4- 1 gallons for every gallon ofchlorinated material. We also addabout 6 pounds of commercialdry sodium formats foreach gallon The ature may be higher or lower.

{of the chlorinated material. The mixture -1s next heated'in a sealed ,container or autoclave to about 160 (3., though the temperbe continuously removed through asuitable weighted valve beyond a fractionating col- .umn. But this is not necessary and we usu-.

ally do not so operate. The retention of the methyl formate in the mixture has the con- Venience that .it allows following the operation'by the indications of a pressure gage.

r During the heating the methyl fornfate produced may At"160, it will be found that ordinarily,

abput six hours heating will bring the reac- ,--tidn to a finish. -The reaction mixture is next cooled or chilled and removed from the insoluble salts, which, as stated, consists mainly of common-salt (sodium chlorid).

'The salt may be washed with a little methyl alcohol to remove any adhering formate and then discarded. Or it may be washed with a small amount of water to extract the forf mate and the dissolved salt and formate separated by crystallization. The liquid removed from the salt dontains some sodium formats in solution but practically no salt.

I This liquid we next distil. The methyl for mate comes over first and should be condensed in an artificially chilled condenser. The excess of methyl alcohol'follows and is also condensed. As stated,- the methyl alcohol and methyl formate may or may not be collected together. If they are collected separately, the methyl formate is heated with a little soda 'or sodium carbonate and the methyl alcohol produced distilled off from the sodium formate which may then be reused. Or the whole mixture of methyl I a substantial residue of saline matter in the chlorinate about 20 .per cent. of the material still which represents the excess of sodium formate employed. This sodium formate may be reused. The amyl alcohol distillate tion are all non-corrosive an formats 1 1. The method of producing high boiling no corrosivemon ohydric alcohols which comprises heating .the. corresponding chlorin compounds .with a mix ture of methyl alcohol anda 2. The process of producing artificial fusel oil which comprises heating a mixture of a monochlorinated lowboiling gasolene fraction with methyl alcohol and a formate.

3. The method of producing high boiling inonohydri'c alcohols which comprises heatmg the corresponding chlorin compounds with a mixture of methyl 'alcohol and a formate under pressure.

4. The process of producing artificial fusel oil whichcomprises heating a mixture of a monochlorinated low boiling gasolene fraction with methyl alcohol and a formate under pressure.

5. The method of producing high boiling monohydric alcohols which comprises heating the corresponding chlorin compounds with a mixture of methyl alcohol and a formate under pressure at a temperature between 140 and 190" C.

6. The process of producing artificial fusel oil which comprises heating a mixture of a monochlorinated low boiling gasolene fraction with methyl alcohol and a formate under pressure at a temperature between 140 and 180 C.

monohydric alcohols,

. 7 In the manufacture of high boiling the process which comprises heating a mixture of a corres onding chlorin compound with methyl a cohol and sodium formate under pressure tilling to obtain methyl formate, methyl alcohol, and the higher boiling alcohol, produced, and a residue representing the excess of the formate employed.

9. Inthe manufacture of high boiling monohydric alcohols, the process which comprises heating a mixture of a chlorinated hydrocarbon corresponding to the alcohol to be obtained with sodium formate and methyl alcohol under pressure at a temperature between 140 and 160 (3., recovering the methyl alcohol and the methyl formate produced as well as the high boiling alcohol formed and treating the methyl formate with soda to reform sodium formate.

Intestimony whereof, we afiix our'signatures hereto.

BENJAMIN 'r. BROOKS.

HARRY ESSEX. 

